The effect of Ti addition on the oxidation resistance of high-purity 19%Cr ferritic stainless steels has been investigated during isothermal heat treatment at temperatures between 1073 K and 1273 K in air. The microstructures of scale and the scale/metal interface were investigated in detail by means of SEM-EBSD and FE-TEM together with μ-EDS.

The Ti addition increases the oxidation mass gains but simultaneously improves the critical temperature of the oxidation resistance. The formed scale is mainly Cr2O3 regardless of the addition of Ti but Ti addition increases the thickness of Cr2O3. Considerable reduction in the grain size of Cr2O3 by Ti addition was recognized, which was inferred to increase the oxidation mass gain due to the easy diffusion through the grain boundary. Furthermore, Ti is oxidized beneath the scale/metal interface as internal complex oxides, such as Al2TiO5 and Al2Ti7O15 because of the small amount of aluminum in the steels used. In a somewhat deeper region from the interface, θ-Al2O3 forms where Ti cannot be oxidized. The oxygen getter effect by Ti atoms is postulated to be responsible for improving the oxidation resistance.

The purpose of this study is to investigate the influence of Nb content of Ti-xNb-7Al alloys (x=20-35 mass%, abbreviated as xNbA) on β (bcc)→α″ (orthorhombic) transformation with tempering through microstructure, isothermal age-hardening, and shape change of a U-shaped specimen with heating. Full α″-martensite structure was obtained on the quenched 20 NbA. With increasing of Nb content, residual β-phase increased, and single β-phase was obtained in the alloys of more than 25 NbA. From the result, the MS temperature commonly decreases with increasing of Nb content. The hardness of 20 NbA and 23 NbA rapidly increased in a few seconds by isothermal aging at 450°C, and the hardness of the alloys of more than 25 NbA abruptly increased after an incubation period for 30-60 s. No compositional distribution between α″ and matrix in the aged 23 NbA was found by STEM-EDS analysis, but the obvious distribution of Nb was detected in 35 NbA. U-shaped specimen of 20 NbA exhibited no shape change by heating. On the other hand, the specimen of 23 NbA composed of β+α″ phases showed the shape recovery (SR) first due to work induced α″→β inverse transformation, then deformed toward the bending direction (SA: shape advance) due to β→α″ transformation. The specimens of more than 28 NbA composed of single β-phase exhibited only SA without SR. The starting temperature of SA (MSA: β→α″) with heating increases with increasing of Nb content. Merging MS (upper) and MSA (lower), it is proposed that the whole MS of xNbA alloy forms a bow shape curve. It is suggested that the low Nb alloys inside the MS curve transform immediately without atom diffusion by tempering at 450°C, but the higher Nb alloys outside the curve need an incubation period to distribute Nb concentration with atom diffusion, and martensitic α″ transformation will abruptly occur in the local domains less than 25 NbA which is the inside of the curve.

In this study, thermal fatigue tests at maximum temperature 1073 K were performed using 13%Cr-Nb-Si and 18%Cr-Nb-Mo steels as representative heat-resistant ferritic stainless steels for automotive exhaust systems. The changes in the microstructure, the crystal orientation and the hysteresis loop during thermal fatigue in the temperature range from 473 K to 1073 K were investigated. As a result of comparing thermal fatigue life under these conditions, 18%Cr-Nb-Mo steel with high temperature strength was found to have a longer thermal fatigue life than 13%Cr-Nb-Si steel. During the thermal fatigue process, the material was softened by reducing of the amount of solute Nb, and the coarsening of Nb precipitation. By this softening, the form of the hysteresis loops changed with the increase in cycles. By considering the softening of the material, the change in the hysteresis loops could be predicted to some extent. Furthermore, by EBSD analysis, it was recognized that the dynamic recovery and recrystallization accompanied by the uniaxial and fine grain formation occurred during the thermal fatigue process. From the viewpoint of change of the microstructure, the thermal fatigue damage was quantified by the ratio of the low-angle grain boundary, and the change of this index with the progress of the cycle in 18%Cr-Nb-Mo steel had a smaller than 13%Cr-Nb-Si steel. It was thought that this point was caused by the retardation of recrystallization by solute Mo.

It is well known that the mechanical strength of iron is significantly changed by alloying. However, atomistic origin and underlying mechanism are still unclear. Since the strength change with respect to solute concentration is very sensitive and highly non-linear, the way of empirical prediction may contribute little to designing the mechanical strength by alloying. In this study, we theoretically construct a model which predicts temperature, strain rate, and solute concentration dependencies on critical resolved shear stress (CRSS) and yield stress of BCC iron alloys with dilute substitutional solutes based on atomistic analysis of the dislocation-solute atom interaction. In the coarse-grained BCC polycrystalline metals, the mechanical strength and deformation are dominated by screw dislocation motion consisting of kink nucleation and migration processes. Thus, our model is based on atomistically computed activation free energies for kink nucleation and migration of screw dislocation. We eventually apply our model to Fe-Si dilute alloy system as a representative example of BCC dilute alloys, and the theoretically predicted CRSS by our model is compared with an experimental one.

The oxidation behavior of Zircaloy-4 at high temperatures in a flowing Ar-H2O (saturated at 323 K) mixed gas was investigated using hydrogen and oxygen sensors installed at a gas outlet, and the utility of the gas sensing methods by using both sensors was examined. The generated amount of hydrogen was determined from the hydrogen partial pressure continuously measured by the hydrogen sensor, and the resultant calculated oxygen amount that reacted with the specimen was in close agreement with the mass gain gravimetrically measured after the experiment. This result demonstrated that the hydrogen partial pressure measurement using a hydrogen sensor is an effective method for examining the steam oxidation of this metal as well as monitoring the hydrogen evolution. The advantage of this method is that the oxidation rate of the metal at any time as a differential quantity is able to be obtained, compared to the oxygen amount gravimetrically measured as an integral quantity. When the temperature was periodically changed in the range of 1173 K to 1523 K, highly accurate measurements could be carried out using this gas monitoring method, although reasonable measurements were not gravimetrically performed due to the fluctuating thermo-buoyancy during the experiment. A change of the oxidation rate was clearly detected at a monoclinic tetragonal transition temperature of ZrO2. From the calculation of the water vapor partial pressure during the thermal equilibrium condition using the hydrogen and oxygen partial pressures, it became clear that a thermal equilibrium state is maintained when the isothermal condition is maintained, but is not when the temperature increases or decreases with time. Based on these results, it was demonstrated that the gas monitoring system using hydrogen and oxygen sensors is very useful for investigating the oxidation process of the Zircaloy in steam.